Synthesis and characterization of electrochemically polymerized metal-free, nickel and zinc containing phthalocyanine derivatives

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2009
Yavuz, Arzu
In the first part of this study, 4-(2,5-di-2-thiophen-2-yl-pyrrol-1-yl)-phthalonitrile (SNS-PN) was synthesized by utilizing 1,4-di(2-thienyl)-1,4- butadione (SOOS) and 4-aminophthalonitrile via Knorr-Paal Reaction. Nuclear magnetic resonance (1H NMR and 13C NMR) and fourier transform infrared (FTIR) spectroscopies were utilized for the characterization of this compound. SNS-PN monomer was then electrochemically polymerized in acetonitrile/0.2 M LiClO4 solvent/electrolyte couple. Characterizations of the resulting polymer P(SNS-PN) were carried out by cyclic voltammetry (CV), UV–vis and FTIR spectroscopic techniques. Spectroelectrochemical studies revealed that P(SNS-PN) has an electronic band gap of 2.5 eV and exhibits electrochromic behaviour. The switching ability of polymer was also monitored. It was also found that P(SNS-PN) was fluorescent and its fluorescence intensity enhanced in the presence of cations. In the second part, novel tetrakis (4-(2,5-di-2-thiophen-2-yl-pyrrol-1-yl)) substituted metal-free (H2Pc-SNS), zinc (ZnPc-SNS) and nickel phthalocyanine (NiPc-SNS) complexes were synthesized and characterized by elemental analysis, FTIR and UV-Vis spectroscopies. The solution redox properties of these complexes were also studied by using CV and differential pulse voltammetry. All of the complexes showed two reversible reduction peaks having ligand-based character and one irreversible oxidation peak. Also, the electrochemical polymerization of these complexes was performed in dichloromethane/tetrabutylammonium perchlorate solvent/electrolyte couple. Resulting polymer films were characterized by UV–vis and FTIR spectroscopic techniques and their electrochemical behaviors were investigated utilizing CV. In-situ spectroelectrochemical investigations revealed that all the polymer films could be reversibly cycled and exhibit electrochromic behavior. Furthermore, the band gap of P(H2Pc-SNS), P(ZnPc-SNS) and P(NiPc-SNS) were calculated as 2.38 eV, 2.25 eV and 2.69 eV, respectively. Moreover, the fluorescence property of the P(ZnPc-SNS) was investigated in dimethyl sulfoxide and toluene.

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Citation Formats
A. Yavuz, “Synthesis and characterization of electrochemically polymerized metal-free, nickel and zinc containing phthalocyanine derivatives,” Ph.D. - Doctoral Program, Middle East Technical University, 2009.